A new approach for photoelectrocatalytic oxidation of NADH is described, based on a graphite electrode (G) modified with a new phenothiazine derivative, polyphenothiazine formaldehyde (PPF). Electrochemical measurements reveal that G/PPF presents a quasireversible voltammetric response, corresponding to a 2e(-)/2H(+) transfer and that G/PPF modified electrodes show electrocatalytic activity for NADH oxidation. When the surface of the G/PPF modified electrode was irradiated with a light source (250 W Halogen lamp), a significant increase in the electrocatalytic current was observed. The second order electrocatalytic rate constant (k(obs,[NADH]=0) = 3.9 x 10(3) M-1 s(-1), pH 7.0) was calculated from rotating disk electrode experiments, performed at various NADH concentrations. From amperometric measurements, it was noticed that, in the presence of light irradiation, the sensitivity of NADH detection (calculated as I-max/K-M ratio) increased ca. 3 times.